Detection of Br and I as atomic anions using liquid sampling – atmospheric pressure glow discharge/Orbitrap mass spectrometry

The quantification and determination of halogen isotope composition is essential in many fields including geochemistry and nuclear forensics. Detection of the halogen elements is commonly attempted with inductively coupled plasma mass spectrometry (ICP-MS) however, there are multiple challenges faced. Most significantly this includes very poor ionization efficiency and the potential for isobaric interferences from either matrix or plasma species. Thus, sensitivity and accuracy are often limiting issues. Here a liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source is coupled with an ultrahigh resolution Orbitrap MS to perform halogen detection of bromine and iodine as initial analytes. This facilitates simple and sensitive detection of these elements as atomic anions from simple aqueous salt solutions. Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) energies were optimized to produce the maximum response of Br⁻ and I⁻. The LS-APGD conditions were optimized using a design of experiments (DOE) approach for Br⁻ and I⁻ concurrently. Response curves for Br⁻ and I⁻ solutions determined limit of detection (LOD) values of 50 pg and 5 pg, respectively, in 20 μL aliquots. The curves indicated response factors of 0.67 for ⁷⁹Br⁻ and 0.90 for ¹²⁷I⁻. Br isotope ratios were determined with precision between 0.7 and 7.3% RSD, with the isotope ratios determined with precision 0.8% RSD at concentrations above the limit of quantification. Preliminary tests were conducted to evaluate the effect of different cations (Na⁺, K⁺, and Mg²⁺) on Br⁻ responses, with no discernible impacts observed on the halogen signal responses. This study demonstrates the potential use of the LS-APGD-Orbitrap-MS for the detection of multiple halogens while avoiding interferences, minimizing sample preparation, and overcoming ionization barriers.